Jurnal MFC
Jurnal MFC
Jurnal MFC
Research paper
a r t i c l e i n f o a b s t r a c t
Article history: This paper describes the potential for algal biomass production in conjunction with wastewater treat-
Received 27 July 2014 ment and power generation within a fully biotic Microbial Fuel Cell (MFC). The anaerobic biofilm in the
Received in revised form anodic half-cell is generating current, whereas the phototrophic biofilm on the cathode is providing the
12 May 2015
oxygen for the Oxygen Reduction Reaction (ORR) and forming biomass. The MFC is producing electricity
Accepted 17 May 2015
Available online 9 June 2015
with simultaneous biomass regeneration in the cathodic half-cell, which is dependent on the nutrient
value of the anodic feedstock. Growth of algal biomass in the cathode was monitored, assessed and
compared against the MFC power production (charge transfer), during this process. MFC generation of
Keywords:
Photosynthetic cathode
electricity activated the cation crossover for the formation of biomass, which has been harvested and
Microbial fuel cell reused as energy source in a closed loop system. It can be concluded that the nutrient reclamation and
Biomass assimilation into new biomass increases the energy efficiency. This work is presenting a simple and self-
Photo-reactor sustainable MFC operation with minimal dependency on chemicals and an energy generation system
Algae utilising waste products and maximising energy turnover through an additional biomass recovery.
© 2015 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
http://dx.doi.org/10.1016/j.biombioe.2015.05.017
0961-9534/© 2015 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
88 I. Gajda et al. / Biomass and Bioenergy 82 (2015) 87e93
done through various configurations [12]. Its operation has an (VWR International) as previously described [16]. The electrode
important additional advantage of using both chambers for material was carbon fibre veil with a total area of 270 cm2 (20 g/m2)
simultaneous treatment under different conditions, which helps (PRF Composite Materials, Poole, UK) used in both the anode and
with the removal of pollutants [13]. For example, incorporating cathode chambers. Carbon veil sheets were folded down into
photosynthetic organisms can provide active electron acceptors for rectangular cuboids and connected with a nickel-chrome wire
the cathode, as well as dissolved oxygen for the ORR [7,14e16]. It (thickness-0.45 mm) to the external circuit. The cathode electrodes
has been previously shown that the cathodic half-cell can be part of were modified in 5 different experimental groups (Table 1) and
a carbon capture system via an open to air configuration [17] where included two control conditions, i.e. one control group with no
carbon capture can be achieved by (i) the mineralisation of CO2 into electrode modification and an abiotic control (algae water) and 4
trona and (ii) the growth of phototrophic organisms in double- experimental groups with: a) non modified cathode electrode
chamber MFCs [18,19]. The use of phototrophs as biocatalysts in (algae); b) cotton string (thickness-2 mm) wrapped around the
the cathode half-cell aims to: (i) meet the oxygen level re- electrode (algae string); c) cellulose layer (thickness-1 mm) coating
quirements for the ORR [14] and (ii) produce biomass that can be around the electrode (algae cellulose); d) stainless steel wire (type
subsequently used directly as the fuel for the MFC anode. Algal 316, thickness 0.45). The modifications were employed to support
powder has been previously shown to be a suitable feedstock for algal biofilm development on the cathode electrode and for current
MFCs [20,21]. Photo-cathodes have been recognised as the most collection. Each experimental condition was tested in triplicate
promising option for incorporation of photosynthesis into MFC resulting in a total of 15 MFCs. No growth media, pH control or
systems [22] and enabling energy production with the added value chemical pre-treatment were used.
of carbon fixation [23]. The key innovation on a large scale would
lay in low cost biomass regeneration and nutrient recovery (such as 2.2. MFC inoculation and operation
nitrogen and phosphorus) for use as fertilisers. However, from the
practical point of view, most microalgal MFC studies contain spe- For the cathode inoculum, fresh pond water (Frenchay, Bristol)
cific, controlled media and growth conditions, and often CO2 was cultivated in a well-illuminated laboratory environment for 2
addition to support algal growth [15,24]. Here, it is proposed that a months prior to the start of experiments, to allow algal growth and
microalgal culture can be maintained in the cathode chamber development. When the sample became visibly green, it was used
simply by the MFC operation, addition of water and exposure to as the inoculum for the cathode half-cell and operated in batch
light. Moreover, the algal culture is of natural origin, may be mode to ensure biofilm establishment and electrode colonisation.
spontaneous and is not controlled or limited. During the MFC Sterilised deionised water was used as the catholyte in the control
operation, cations other than protons are being transported from MFCs. Anodes were inoculated with activated anaerobic sludge
the anode to the cathode through a PEM [25], which is a mecha- provided by the Wessex Water Scientific Laboratory (Saltford, UK),
nism that may support algal micronutrient requirements to sustain mixed with 0.1 M sodium acetate prior to use (pH 7.2) and
and enhance algal growth. This experimental work is presenting employed thereafter for periodic feeding. After 40 days, each of the
the further development of previously published work on photo- cathode chambers was connected to the 0.5 L Schott photoreactor
synthetic cathodes [16] and the lagooning photosynthetic ponds bottles in which, again algae were re-suspended in fresh pond
[26]. The advantages of algal cathodes include eliminating the need water. The photoreactor bottles were connected via a 16-channel
for a mechanical air supply at the cathode therefore lowering the peristaltic pump (205U, Watson Marlow, UK) to the MFCs in a
running costs and reducing the overall CO2 emissions from the closed loop recirculation manner, at a flow rate of 123 mL/h, as
anodic bacterial respiration. Dual-chamber MFCs were evaluated shown in Fig. 1. The MFCs and photoreactor bottles were placed in a
under batch-fed mode using sewage sludge and sodium acetate as temperature- and light-controlled incubator (LMS Ltd., Kent, UK),
the carbon-energy source, with mixed anaerobic bacteria as the fitted with two Cool White Daylight Tubes (3500 lux), and
anode biocatalyst. The cathode compartment contained mixed controlled by a programmable timer under a 14 h light/10 h dark
photosynthetic consortia. The cathode chamber was connected to regime at 22 C.
photo-reactors, which acted as oxygen reservoirs/photosynthetic MFCs were operated under 8.2 kU external resistive loads for 8
ponds. Algal biomass produced in the cathodic photoreactors has months while the cathode half cells as well as the photoreactors
been harvested and used directly as fuel in the anode, thereby showed visibly established green communities. Microscopic
closing the loop and demonstrating self-sustainability. Unlike observation showed a dominant community of green algae and
previous work, the algal biomass was fed neat, i.e. it has not been other species such as cyanobacteria, heterotrophic bacteria and
processed or dried. Furthermore, the system has not used any CO2 protozoa. During the long-term MFC operation, the control (abiotic)
fertilisation, pH control, growth media, catalysts, exotic metals, cathodes became serendipitously biotic, showing growth of
compressed air mixing or externally forced air-flow to optimise and photosynthetic organisms visible to the naked eye in the chambers
simplify MFC conditions in order to present its suitability for future as reported earlier [16]. All MFCs have shown a well-developed
practical applications. photosynthetic biofilm in the cathode side half-cell. This is when
This work is aiming to: i) demonstrate the operation of a fully all the photoreactors were filled with fresh deionised water and the
biological microbial fuel cell with an anaerobic anode and a photo- growth of photosynthetic organisms was observed and assessed as
synthetic cathode colonised by the mixed culture of photosynthetic shown in Fig. 1.
organisms; ii) investigate the relationship between the development
of the cathodic biofilm and MFC power generation and iii) utilise the 2.3. Data capture
harvested biomass directly as a feedstock for the MFC anodes.
Polarisation experiments were performed using a resistorstat
2. Materials and methods tool [27] in the range of 30 kU to 10U and the time constant for each
resistance value was 3 min. Data were logged using an ADC-24 16-
2.1. MFC design Channel Data Logger (Pico Technology LTD., Cambridgeshire, UK).
The data were processed using the Microsoft Excel and GraphPad
MFC reactors comprised 25 mL anode chambers and 25 mL Prism software packages. Current and power were calculated as
cathode chambers, separated by a cation exchange membrane previously described [28].
I. Gajda et al. / Biomass and Bioenergy 82 (2015) 87e93 89
Table 1
Electrode modifications in the cathode biotic and abiotic environment.
Algae water Carbon veil (control) (Initially) abiotic e (subsequently) turned biotic
Algae Carbon veil Biotic
Algae string Carbon veil wrapped with cotton string Biotic
Algae cellulose Carbon veil wrapped with cellulose coating Biotic
Algae wire Carbon veil wrapped with stainless steel wire Biotic
Fig. 1. Microbial Fuel Cell (MFC) with a biomass harvesting photoreactor. The source of fuel was organic waste (sludgeþ20 mM sodium acetate) or biomass harvested from the
cathodic photoreactor.
2.4. Biomass assessment and algae cellulose 61 mW maximum power in comparison with the
abiotic MFC (control) with the lowest performance of 46 mW. The
A direct microscopic count was performed on the harvested results are consistent with previously reported data, where the
samples of microalgal suspension using a Neubauer bright line algae were shown to improve the system power performance and
haemocytometer (Marienfeld, Germany) and a transmitted light longevity [16]. The biomass accumulation in the connected to the
microscope (Axiostar Plus, Carl Zeiss) 4 weeks after the start of the MFC photoreactors, shows dependence on the charge transfer of
experiment. Optical density was measured using a 6300 spectro- the MFCs and can be directly linked with the produced power.
photometer (Jenway, UK) at 678 nm (Chl a absorption peak). Therefore it is suspected that the more electricity the MFC gener-
Microalgal dry weight (mg/L) was assessed using a vacuum filtra- ates, the more biomass may be obtained from its cathode photo-
tion unit (Millipore, UK) and 47 mm (0.2 mm pore size) sterile reactor. The harvested biomass showed that the cell density for the
membrane filters (Whatman, VWR, UK). Dry weight was deter- algal cathode was up to 31 107/L. A platinum based cathode was
mined by the analytical balance (HR120, Metler Toledo) after previously shown to maintain a monoculture of Chlorella vulgaris
obtaining constant weight from drying filter papers for 24 h under [18] for CO2 sequestration and oxygen generation. Here not only the
room temperature and 1 h under 100 W lamp. Calibration was same process is supported but it is further hypothesised that the
performed using dilutions in the range of dilution factor (DF) of 1- cationic flux of ions such as NH4þ through the exchange membrane,
0.1. which is dependent on the MFC performance, can influence
biomass growth [29] in a carbon based MFC system. This can
2.5. Cathode surface analysis significantly lower the cost of MFC technology making it feasible for
practical applications.
Surface morphology image of cathode electrodes with the
attached photosynthetic biofilms, was observed by scanning elec- 3.2. Algal growth within the reactor
tron microscopy (SEM). Dry samples were mounted on aluminium
using contact adhesive. Images were observed and captured using a The relationship between optical density, cell density and dry
Philips XL30 scanning electron microscope (SEM). Samples were weight was established by linear regression, as shown in Fig. 3
further prepared for microscopy by sputter coating in gold using an (left). As the samples were taken from the photoreactor bottles, it
Emscope SC500. was observed that algae, algae wire and algae water showed uni-
form cell densities, whereas more aggregation was observed in the
3. Results & discussion string and cellulose units. The aggregation in the MFC with string
and cellulose was limiting the optical density measurement as a
3.1. MFC power performance reliable tool of biomass assessment. Therefore, the dry weight was
chosen to correlate with the maximum power performance (Fig. 3,
The maximum absolute power generation is shown in Fig. 2, right). Microalgal biomass growth at the cathode was assessed to
where the best performing MFC was the algal based cathode giving correlate with the power output. It shows that the most promising
128 mW, algae water 81 mW, algae string 74 mW, algae wire 67 mW configuration for the algal cathode is the non-coated carbon veil
90 I. Gajda et al. / Biomass and Bioenergy 82 (2015) 87e93
Fig. 3. Calibration curves of optical density at A678, cell density and biomass (left). Relationship between the harvested biomass from the photoreactors and MFC power per-
formance (right).
matrix to allow better diffusion of dissolved oxygen to the could be one very cost-effective option for future scale-up. The co-
electrode. existence of the attached biofilm, suspended biomass in solution
The high cost of CO2 as a feedstock for algal growth is a major and aggregate forming, made it difficult to accurately quantify the
obstacle, which is why there is interest in CO2 regeneration tech- total biomass with optical density or haemocytometer. Analyses
niques [30] and algal growth has already been correlated with were performed on the least aggregated samples however the
power performance in a wastewater supplemented cathode [31]. In highest aggregation was observed in the cellulose and string based
the present study, it is suggested that the cathode acts more like a cathodes, which might be due to the dense electrode colonisation
polishing chamber, since no other nutrients were supplied, other as shown in Fig. 4.
than naturally occurring pond water (inoculum) and deionised Surface texture is one of the factors that influence microalgal
water. attachment to different substrata. In general, rough or porous sur-
faces have higher surface area and better cell attachment, and are
thus preferred as natural substrata for algae harvesting [38]. It has
3.3. Photosynthetic biofilm
been observed that the biomass growth was the lowest in the algae
wire MFCs, and may be related to stainless steel bio-corrosion
The SEM images (Fig. 4) show algal biofilm formed on all tested
affecting the output and limiting algal growth. Microscopic obser-
cathode electrodes in comparison with the abiotic control. String
vation had shown a predominant colonisation by unicellular as well
and cellulose coating showed a layer consisting of microorganisms
as mixed algae and cyanobacteria, bacterial species and protozoa
embedded in a microbial extracellular polymeric substance (EPS)
suggesting it is a dynamic and balanced close-to-natural ecosystem.
matrix formed on the electrode surface. The thicker biofilm formed
Natural biofilm communities include a number of microbes such as
in these two conditions possibly limited the oxygen diffusion and
fungi, algae, protozoa and bacteria showing symbiotic interactions
MFC performance as indicated before [32], which suggests that the
[39]. The development of a natural and low maintenance biocathode
power generation as well as biomass production is favoured up to a
for active biomass fixing will help to make MFCs a carbon-neutral
certain thickness of photosynthetic biofilm on the cathode.
technology with enhanced efficiency and self-sustainability.
Oxygenic biofilm has already been shown to enhance the MFC
I. Gajda et al. / Biomass and Bioenergy 82 (2015) 87e93 91
Fig. 4. SEM images of cathode electrodes with developed biofilm (b, d, e, f) and abiotic control electrode (a) which spontaneously turned biotic (c).
3.4. Algae used as feedstock comparison to acetate, is indicating that algal biomass seems to be a
more complex substrate due to its mineral composition.
The catholyte collected from the photoreactors was harvested A similar closed loop system was already presented [40] where
and separated into 4 feedstock solutions dependent on the type and an Anaerobic Digester had been supplied with algal feedstock in a
the amount of biomass: non aggregated feedstock whose biomass pre-treatment stage. The proof of concept has been presented in
content was: a) 0.25 g/L, b) 0.39 g/L and aggregated feedstock: c) strictly controlled conditions and supplemented with growth me-
dry mass 0.56 g/L d) dry mass 0.72 g/L. The biomass was used as dia and CO2 fertilisation. Here these control mechanisms were
feedstock directly without any pre-treatment. The graph in Fig. 5 avoided to represent the sustainable MFC utilising natural pro-
shows the average power of all five types of MFC when fed with cesses. In this set up the control environment was minimised to
sludgeþ0.1 M acetate in comparison with algal feedstock used as show the possibility of implementation in real world applications.
indicated. It shows that the algal feedstock produced by the MFC Algae are produced in abundance in high-rate algal oxidation ponds
cathode may be successfully utilised as the anodic substrate. The from the tertiary phases of the sewage treatment process [41].
performance increased with the amount of biomass fed to the Algae have previously been used as feedstock for MFCs as powders
anode half-cell. The slow-release nature of this feedstock (Fig. 6) in [20,21], or pre-treated microalgae [42] and macroalgae [43].
Fig. 5. Algal biomass used as feedstock in comparison to acetate used at the beginning of the test.
92 I. Gajda et al. / Biomass and Bioenergy 82 (2015) 87e93
Phototrophic biofilms grow in response to light, carbon dioxide and Research Council UK grant numbers EP/I004653/1 and EP/L002132/
inorganic nutrients where the availability of nutrients influences 1. The authors would like to thank Dr Man-Kim Cheung and Dr
the type of biofilm formed [44]. Third generation biofuels from David Patton from the University of the West of England for their
algal cells grown on non-arable land provide a solution in the food- valuable help and expertise.
fuel debate [45]. Wastewater seems to be the best option for
reducing the environmental burden from the cultivation of algal
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